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Two planar type photovoltaic polymers based on naphthobisthiadiazole, poly(2,5-bis(2-hexyldecyloxy)phenylene-alt-(5,10-dithiophen-2-yl)naphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole) (h-PPDTNTz) and poly(2,5-bis(2-decyltetradecyloxy)phenylene-alt-(5,10-dithiophen-2-yl)naphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole) (d-PPDTNTz) were synthesized by incorporating intrachain noncovalent Coulombic interactions in the molecular design. To achieve a delicate balance of molecular weight, solubility as well as bulk film morphology, hexyldecyloxy (h-) and decyltetradecyloxy (d-) side-chains were substituted, which played a decisive role in modulating morphology, film packing structure and macroscopic device properties. Both polymers showed a broad light absorption up to ~800 nm and d-PPDTNTz exhibited a deeper HOMO and preferentially face-on orientation in pristine and blended films with PC71BM. The detailed optical, electrochemical, thermal, morphological and the resulting photovoltaic characteristics were studied. The best power conversion efficiency of ~6.7% was measured for d-PPDTNTz:PC71BM, suggesting that the careful choice of side-chains is necessary for fully optimize the photovoltaic materials and devices.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Improvement of the power conversion efficiency and long term stability remains to be of crucial importance for the further development of polymer solar cells (PSCs). Herein, a donor-acceptor copolymer based on 4,8-di(thiophene-2?-yl)benzo[1,2-b:4,5-b?]dithiophene (DTBDT) and 4,7-di(thiophene-2?-yl)benzo[c][1,2,5]thiadiazole (DTBT), specifically selected because of its suitability for roll-coating in the ambient environment, is investigated in terms of operational stability via partial exchange (5 or 10%) of the alkyl side chain on either the donor or the acceptor monomer with a 2-hydroxyethyl or 2-phenylethyl group. It is shown that the exchange of the hexyl chain on the DTBT moiety has a negative impact on the stability of the polymer as well as on the performance of the resulting PSCs. On the other hand, partial exchange of the 2-hexyldecyl side chain of the BDT unit by a 2-hydroxyethyl group results in an improved photochemical stability of the polymer film and a higher efficiency of 5.6% for the spin-coated PSC. The stability of roll-coated devices also slightly increases with the incorporation of 10% of either the 2-hydroxyethyl or 2-phenylethyl side chain.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The Pd-catalyzed coupling of gamma-hydroxyalkenes with aryl bromides affords enantiomerically enriched 2-(arylmethyl)tetrahydrofuran derivatives in good yield and up to 96:4 e.r. This transformation was achieved through the development of a new TADDOL/2-arylcyclohexanol-derived chiral phosphite ligand. The transformations are effective with an array of different aryl bromides, and can be used for the preparation of products bearing quaternary stereocenters.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Compounds that modulate the estrogen receptor (ER) are disclosed, as well as pharmaceutical compositions containing the same. In a specific embodiment, the compounds are selective for ER-beta over ER-alpha. Methods are disclosed for modulating ER-beta in cell and/or tissues expressing the same, including cells and/or tissue that preferentially ER-beta. Methods for treating estrogen-related conditions are also disclosed, including conditions such as is breast cancer, testicular cancer, osteoporosis, endometriosis, cardiovascular disease, hypercholesterolemia, prostatic hypertrophy, prostatic carcinomas, obesity, hot flashes, skin effects, mood swings, memory loss, urinary incontinence, hairloss, cataracts, natureal hormonal imbalances, and adverse reproductive effects associated with exposure to environmental chemicals.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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In this study two donor-acceptor type alternating polymers containing electron-deficient benzotriazole moiety and electron-rich selenophene bearing benzodithiophene moiety; P1 and P2, were designed and synthesized via Stille polymerization. Moreover, the effects of thiophene and selenophene as pi-bridges on optical, electrochemical and optoelectronic features of polymers were examined. The optical band gap values of P1 and P2 were found as 1.47 eV and 1.72 eV, respectively. Cyclic voltammetry studies were performed to investigate the electrochemical properties of polymers. The HOMO and LUMO energy levels of P1 and P2 were recorded as ?5.45/?3.09 eV and ?5.49/?3.21 eV, correspondingly. Optical, electrochemical and optoelectronic studies of P1 and P2 demonstrated that both two polymers were suitable to be utilized as donor materials for bulk heterojunction organic solar cell applications. Photovoltaic properties were investigated ITO/PEDOT:PSS/Polymer:PC71BM/LiF/Al device structure measured under standard AM 1.5 G illumination (100 mW/cm2). As a consequence of photovoltaic measurements, the highest power conversion efficiency values were recorded as 2.41% for P1:PC71BM (1:2) (w/w) based device with a VOC 0.83 V, a JSC 5.66 mA/cm2, and fill factor of 51.22% values.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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An unprecedented asymmetric allenylic alkylation of readily available imine esters, which was enabled by a synergistic Cu/Pd catalysis, has been developed. This dual catalytic system possesses good substrate compatibility, delivering a diverse array of nonproteinogenic alpha-allenylic alpha-mono- or alpha,alpha-disubstituted alpha-amino acids (alpha-AAs) with high yields and generally excellent enantioselectivities. Furthermore, the scalability and practicability of the current synthetic protocol were proven by performing gram-scale reactions and by the first catalytic asymmetric synthesis of naturally occurring (S)-gamma-allenic alpha-amino acid, respectively.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A palladium-catalyzed coupling of allylic carbonates with trimethylsilylisocyanate to provide allylic isocyanates is reported. Amines are added in a second step to yield allylic ureas in this one-pot procedure. Use of a bidentate phosphine ligand with a large bite angle was found to be important in this transformation. The scope of allylic carbonates has been examined, as well as amines compatible with these reaction conditions.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Halogenation, for example, fluorination and chlorination, is an effective strategy to regulate the performance of organic photovoltaic materials. Although fluorination has been widely applied to polymer acceptors, systematic studies on the comparison of nonhalogenated, fluorinated, and chlorinated polymer acceptors have been a blank to now. Herein, a B ? N embedded electron-deficient unit (A), namely, BNIDT was copolymerized with three electron-rich units (D), that is, benzodithiophene (BDT), fluorinated BDT, and chlorinated BDT to obtain three D-A polymers of BN-BDT, BN-BDT-F, and BN-BDT-Cl, respectively. The three polymers exhibit similar LUMOs of ca. -3.77 eV, whereas the HOMOs are remarkably decreased from BN-BDT (-5.46 eV) to BN-BDT-F (-5.71 eV) and further slightly lowered to BN-BDT-Cl (-5.74 eV). All-polymer solar cells (all-PSCs) were fabricated using PBDB-T as the donor and the three B ? N-based polymers as the acceptors. The efficiencies of all-PSCs were significantly promoted from nonhalogenated BN-BDT (1.60%) to fluorinated BN-BDT-F (3.71%) and further elevated to chlorinated BN-BDT-Cl (4.23%). Device characterizations revealed that halogenation on the polymer acceptors leads to enhanced hole-transfer driving forces and better donor/acceptor miscibility, for example, smaller domain sizes and root-mean-square roughness (rms) values, which further gives rise to higher and more balanced hole/electron mobilities and efficient physical processes, for example, efficient exciton dissociation and collection and weaker recombination losses in halogenated devices. This work demonstrates that the photovoltaic performance of nonhalogenated polymer acceptors can be remarkably boosted by fluorination and further enhanced by chlorination. This is the first systematic study on the halogenated polymer acceptors by comprehensively comparing nonhalogenated, fluorinated, and chlorinated ones.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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N-(Naphthyl)-4-R-salicylaldimines (R = OCH3, H and Cl; H2L1-H2L3) and 2-hydroxy-N-(naphthyl)naphthaldimine (H2L4) readily undergo, upon reaction with Na2[PdCl4] in the presence of triphenylphosphine, cyclopalladation via C-H bond activation at the peri-position to afford complexes of type [Pd(L)(PPh3)] (L = L1-L4). The C-H bond activation has been found to be mediated by palladium(0) formed in situ. A similar reaction of H2L1 with Na2[PdCl4] in the presence of 1,2-bis(diphenylphosphino)ethane (dppe), in a 2 : 2 : 1 mole ratio, yields a dinuclear complex of type [{Pd(L1)}2(dppe)]. Reaction of H2L1 with Na2[PdCl4] in the presence of 4-picoline (pic) yields [Pd(L1)(pic)]. The molecular structures of the six complexes have been determined by X-ray crystallography. The aldiminate ligand in each compound is coordinated to the metal center as a di-anionic tridentate ONC-donor, with the fourth coordination site occupied by a phosphine or picoline ligand. The new complexes show intense absorptions in the visible and ultraviolet regions, and the nature of the optical transitions has been analyzed by TDDFT calculations. The palladium complexes display notable efficiency in catalyzing C-C and C-N bond coupling reactions. The thermodynamics for the formation of the cyclometalated catalyst precursor [Pd(L2)(PPh3)] has been evaluated by DFT calculations.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A versatile and general catalytic strategy has been developed for the alpha-arylation of phosphonoacetates utilizing parallel microscale experimentation. These alpha-substituted phosphonoacetates are widely useful, notably as substrates in the Horner-Wadsworth-Emmons-type olefinations. However, the current routes to these products involve harsh conditions, limiting the variety of functionality. The reported method can be used with a variety of aryl chlorides and aryl bromides, including several heterocyclic examples.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method